Fractionnement et caractérisation de la matière organique des lixiviats de décharges d'ordures ménagères

Les lixiviats de décharge constituent une source de nuisance qui vient s'ajouter aux nombreux problèmes de contamination du milieu environnant s'ils ne sont pas traités avant leur rejet. La matière organique, principale composante de ces effluents, doit retenir une grande attention dans la mesure où il est difficile d'éviter la propagation et la diffusion de cette pollution dans les sols et vers les nappes phréatiques. Cette étude vise à fractionner et à caractériser la matière organique présente dans des lixiviats de décharges d'ordures ménagères afin de prévoir et d'orienter le choix des traitements les plus adaptés compte tenu de leur biodégradabilité.La méthode de fractionnement utilisée comprend une adsorption spécifique sur résines macroporeuses Amberlite XAD (combinaison de XAD-7 et XAD-4) pour séparer les composés hydrophobes et hydrophiles qui sont ensuite extraits à la soude (composés acides) et au dichlorométhane (composés neutres). Le fractionnement de la matière organique par filtration sur résines XAD-7 et XAD-4, après une première étape de précipitation en milieu acide (pH=1), a permis de répartir l'ensemble des composés organiques du lixiviat dans six fractions de spécificités différentes fonction de la taille et/ou du caractère hydrophile ou hydrophobe des molécules. Les résultats montrent que ce protocole expérimental permet d'extraire au moins 98 % de la matière organique totale (pourcentage relatif aux teneurs de la demande chimique en oxygène ou DCO), dont la plus grande proportion est constituée des substances humiques (76 % à 90 % en DCO). Diverses méthodes analytiques ont été proposées en vue de caractériser les fractions isolées telles que l'analyse élémentaire, la spectrophotométrie infrarouge, la résonanoe magnétique nucléaire C13 (RMN Cl3) et la chromatographie CG/FID et CG/SM.Landfill leachates represent an obvious source of pollution for the environment and many studies have attempted to analyze organic pollutants found in leachates. A number of methods have been described in the literature for the isolation and concentration of dissolved organic matter from landfill leachate samples. Membrane ultrafiltration, gel permeation and high performance liquid chromatography are commonly used because these techniques can be easily adapted to separate soluble organic substances from large volumes of leachate. The objective of this study was to fractionate and characterize dissolved organic matter found in leachates collected from sanitary landfills.The discharges are defined with regard to the geological context from which they are situated and the nature of the waste. The discharges are classified in three categories, based upon the value of the permeability coefficient K, the substratum and its continuity.- class 1; impermeable site (K 10-[sup]6 ms-¹). The studied leachates come from landfill of class 2:- Crézin (Haute-Vienne) of compacted type: it was used for household rubbish and assimilated ordinary wastes. - Foussais-Payre (Vendée): leachate coming from the fermentation area of a composting plant and from the compost refuse. Fractionation of dissolved organic matter was applied on three leachates samples. The first sample was the raw leachate collected from the Crézin landfill and the two others came from Foussais-Payre (a raw sample and a sample treated in an aerated lagoon for 52 days). Because of the wide variety of organic compounds that can be found in such leachates, we classified and isolated the different groups of organic constituents using an XAD resin adsorption procedure. The experimental method consisted of acidifying samples to pH 1 to isolate the first fraction (fig. 1) and then treating the remaining supernatant with XAD-7 and XAD-4 resins. The adsorption on XAD resins allowed the isolation of the other organic fractions (figs. 2 to 6). Various analytical techniques were applied to characterize the isolated fractions such as elementary analysis infrared spectroscopy, ¹3C nuclear magnetic resonance (¹3C CP/MAS NMR), gas chromatography (GC/FID), and gas chromatography coupled to mass spectrometry (GC/MS). Results showed that more then 90% of the total organic carbon (TOC) in leachates can he recovered by the isolation procedure. Most of the isolated compounds corresponded to humic substances (76% to 90% of the chemical oxygen demand). Hydrophobic and hydrophilic neutral compounds were found only in small concentrations

Adsorption des métaux lourds (Cu, Zn, Cd et Pb) par les sédiments superficiels d'un cours d'eau: rôle du pH, de la température et de la composition du sédiment

Une étude expérimentale concernant l'adsorption des métaux lourds Cu, Cd, Zn et Pb par des sédiments d'un cours d'eau pollué par des rejets industriels a été entreprise pour mettre en évidence l'importance de certains paramètres expérimentaux, notamment le pH, la masse de sédiments et la température. Elle a permis également d'analyser la nature des liens qui participent à la fixation des cations métalliques sur les différentes fractions sédimentaires déterminées selon la méthode de TESSIER et al. (1979) et d'interpréter les capacités d'adsorption relativement variables suivant la nature du métal. Les résultats confirment le rôle particulier des fractions réductible (oxydes de fer et de manganèse) et organique (substances humiques en particulier), dont les propriétés respectives d'échange d'ions et de complexation ont été souvent vérifiées. La capacité d'adsorption de ce sédiment a notamment pu être interprétée en termes d'isothermes d'adsorption en exploitant les modèles de Langmuir et de Freundlich et leurs équations linéarisées.In an experimental study of the adsorption of Cu, Cd, Zn and Pb by surface sediment in a small stream polluted by the industrial drain of electro-refinery, we have demonstrated the irnportance of some such experimental parameters as pH, sediment concentration and temperature. These experiments were conducted in batch systems at constant temperature with continuous agitation, using a mixture of sediment and metals at an adjusted pH; the quantity of metals remaining in solution was determined by a polarographic method. Adsorption percentages for the concentratons of sediment (200 and 1000 mg/L) and metals (1 mg/L) reached the following maximum values: Pb (99-l00%o), Zn (80-90 %), Cd (75-85 %) and Cu (70-80%). These variations in metal soprtion are attributed to differences in binding energy between the metallic cation and the sediment sites, when all other parameters are fixed. Based on metal partitioning among the different sedimentary fractions, as determined according to the sequential extraction method of TESSIER et al. (1979), it was possible to attribute metal adsorption to complexation, coprecipitation and complexation reactions respectively with organic matter, carbonates and Fe-Mn oxides or alumino-silicates. Our results highlight the specific roles played by the reducible Fe-Mn oxides and by humic substances. Fulvic and humic acids, which are considered as the stable fraction of sedimentary organic matter, can form complexes and participate in the fixation of metals on the sediments (GODFRIN and BLADEL, 1990; WILLIAM and HANSON, 1979; FITCH et al., 1968; BIZRI et al., 1985). The stability of these complexes depends on the variety of reaction sites in these macromolecules, which in turn determines the degree of fixation of the cations (specific adsorption). Concerning the iron-manganese oxides and the alumino-silicate compounds, their surface sites are engaged insurface complex formation by a mechanism of proton exchange in which humic substances can be also involved (BELZILE et al., l989a; BELZILE and TESSIER, 1900; BELZILE et al., 1989b).Adsorption kinetics for Cu, Zn and Cd were relatively fast with more than 50 % of the metal adsorbed in a few hours, followed by a partially reversible stage over the next few days leading to an equilibrium state. Reversibilty of Pb binding was not signifrcant (attributed to the chemical precipitation of Pb3(PO4)2). An enhancement of adsorption with increasing pH between 5 and 8 was noted for Cu, Zn and Cd. Several factors may contribute to this increase in the quantity of absorbed metals:-the M+ and MOH+ species berome more competitivethan H+ fortte adsorption sites on the sediment;- the number of adsorption sites increases;- the change in conformation of the humic substances, from aggregated to stretched forms, may render the metal complexing sites more accessible;- the rate of Fe(III) and Mn(IV) formation is more significant at higher pH values;- at higher pH, the precipitation of oxides, hydroxides and hydroxycarbonates becomes important as well as the adsorption on the suspended phases;- the degree of oxide crystallization is influenced by the pH value and hence the adsorption capacity of reducible phases is also affected.A decrease in metal adsorption was also observed as the temperature increased between 10°C and 40°C. The adsorption of metals was described using FREUNDLICH and LANGMUIR equations in their linear form

La mise à l'équilibre des eaux tropicales : conséquences sur la déferrisation

L'étude de l'équilibre calco-carbonique d'une eau souterraine de l'Afrique de l'Ouest par la méthode de LEGRAND et POIRIER, a conduit à la détermination des conditions de traitement pour neutraliser l'agressivité naturelle de l'eau, due essentiellement à une forte teneur en acide carbonique et réduire ainsi son caractère corrosif. le problème de l'évolution du fer présent en relation avec la mise à l'équilibre a été également étudiée.L'application réalisée sur un pilote de laboratoire a permis d'optimiser les principales étapes du traitement, c'est-à-dire l'addition d'une base forte, la précipitation et la filtration des hydroxydes ferriques qui se forment à la suite de la neutralisation de l'acide carbonique.Studies on calcium carbonate equilibrium of West African ground water, a sample of potable water distributed in Lomé (Togo), were carried out using the method described by LEGRAND and POIRIER. It is a standard graphic method in which calculations include all basic (Ca++, HCO3-, CO3--, CO2, H2O+, OH-), and characteristic (Mg++, Na+, K+, SO4--, Cl- ...) chemical parameters of natural water. Processing of a computer program for calculations enabled the equilibrium and saturation curve [CO2] = f[Ca++], to be obtained. The aggressivity to the lime deposit character, different conditions of treatment, aeration, and addition of an appropriate base to neutralise the nature aggressivity of water due to its high dissolved carbon dioxide content could also be defined.The problem of the presence of iron was studied; high concentration of iron in natural ground water lead to various problems : developing of tastes, staining and discoloration of clothes, and growth of iron bacteria in the distribution system. Its removal from water is accomplished by means of the oxidation of iron (II) to iron (III) followed by the precipitation of relatively insoluble ferric hydroxide. The oxidation rate is highly dependent on pH. Thus, the process of removal of carbon dioxide by stripping or neutralisation raises the pH of the water. If the pH is raised high enough, an insoluble form of iron will precipitate. Another important aspect of the chemical behaviour of iron is the formation of complex ions with inorganic as well as organic ligands; silica in water forms a relatively stable complex with iron (III). The difficulty in removing iron from water is often associated with this phenomenon.Continuous flow studies were carried out to improve important steps of treatment such as addition of a strong base, and precipitation and filtration of ferric hydroxide produced during carbonic acid neutralization. They show the weak stability of silicato-iron (III) complex at high pH value and prove that practically complete iron removal may be obtained

Composting of urban solid waste in Lomé, Togo: Fate of some heavy metals (Ni, Cu, Zn, Pb and Cd)

Metals may constitute problems in waste management because of their multiple sources and potentially high toxicity of some constituents.  Processes of composting do not always guarantee acceptable quality of the compost in terms of hazardous metals. The aim of this article is to assess the balance of some heavy metals during the composting of different categories of urban waste. The fraction of the super fines, i.e. with a particle size of less than 10 mm, contributes 30 to 56% of the total, average contents of metals in  compost. Sorting of waste into various fractions such as plastics, hazardous materials, glass, miscellaneous combustible material, metals, and super fines lowers the metal contents in finished compost by about 80%. The remaining 20% can be washed during the fermentation of windrows or, still better, can be reduced by chemical complex formation in the compost as shown by the leaching adequate test.Keywords: Heavy metals, composting, leaching test

Inequivalent representations of commutator or anticommutator rings of field operators and their applications

Hamiltonian of a system in quantum field theory can give rise to infinitely many partition functions which correspond to infinitely many inequivalent representations of the canonical commutator or anticommutator rings of field operators. This implies that the system can theoretically exist in infinitely many Gibbs states. The system resides in the Gibbs state which corresponds to its minimal Helmholtz free energy at a given range of the thermodynamic variables. Individual inequivalent representations are associated with different thermodynamic phases of the system. The BCS Hamiltonian of superconductivity is chosen to be an explicit example for the demonstration of the important role of inequivalent representations in practical applications. Its analysis from the inequivalent representations' point of view has led to a recognition of a novel type of the superconducting phase transition.Comment: 25 pages, 6 figure

Deux cas de freemartinisme chez des moutons Romanov (Ovis aries)

International audienc

The Importance of Time Congruity in the Organisation.

In 1991 Kaufman, Lane, and Lindquist proposed that time congruity in terms of an individual's time preferences and the time use methods of an organisation would lead to satisfactory performance and enhancement of quality of work and general life. The research reported here presents a study which uses commensurate person and job measures of time personality in an organisational setting to assess the effects of time congruity on one aspect of work life, job-related affective well-being. Results show that time personality and time congruity were found to have direct effects on well-being and the influence of time congruity was found to be mediated through time personality, thus contributing to the person–job (P–J) fit literature which suggests that direct effects are often more important than indirect effects. The study also provides some practical examples of ways to address some of the previously cited methodological issues in P–J fit research

HDX and Native Mass Spectrometry Reveals the Different Structural Basis for Interaction of the Staphylococcal Pathogenicity Island Repressor Stl with Dimeric and Trimeric Phage dUTPases

The dUTPase enzyme family plays an essential role in maintaining the genome integrity and are represented by two distinct classes of proteins; the β-pleated homotrimeric and the all-α homodimeric dUTPases. Representatives of both trimeric and dimeric dUTPases are encoded by Staphylococcus aureus phage genomes and have been shown to interact with the Stl repressor protein of S. aureus pathogenicity island SaPIbov1. In the present work we set out to characterize the interactions between these proteins based on a range of biochemical and biophysical methods and shed light on the binding mechanism of the dimeric φNM1 phage dUTPase and Stl. Using hydrogen deuterium exchange mass spectrometry, we also characterize the protein regions involved in the dUTPase:Stl interactions. Based on these results we provide reasonable explanation for the enzyme inhibitory effect of Stl observed in both types of complexes. Our experiments reveal that Stl employs different peptide segments and stoichiometry for the two different phage dUTPases which allows us to propose a functional plasticity of Stl. The malleable character of Stl serves as a basis for the inhibition of both dimeric and trimeric dUTPases